CN117125897A - Microcrystalline glass, reinforced glass, preparation method and application thereof - Google Patents
Microcrystalline glass, reinforced glass, preparation method and application thereof Download PDFInfo
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- CN117125897A CN117125897A CN202311109673.6A CN202311109673A CN117125897A CN 117125897 A CN117125897 A CN 117125897A CN 202311109673 A CN202311109673 A CN 202311109673A CN 117125897 A CN117125897 A CN 117125897A
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- 239000011521 glass Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 49
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 25
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 25
- 239000011029 spinel Substances 0.000 claims abstract description 25
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 23
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 26
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052642 spodumene Inorganic materials 0.000 claims description 17
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 16
- 239000000156 glass melt Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 239000006058 strengthened glass Substances 0.000 claims description 8
- 239000006121 base glass Substances 0.000 claims description 7
- 239000005341 toughened glass Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 52
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 40
- 239000000395 magnesium oxide Substances 0.000 description 26
- 235000012245 magnesium oxide Nutrition 0.000 description 26
- 239000011787 zinc oxide Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 15
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002791 soaking Methods 0.000 description 9
- 235000010333 potassium nitrate Nutrition 0.000 description 8
- 239000004323 potassium nitrate Substances 0.000 description 8
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 2
- 229910003251 Na K Inorganic materials 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 229910010100 LiAlSi Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- -1 magnesium aluminum silicon Chemical compound 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to microcrystalline glass, reinforced glass, and a preparation method and application thereof. The microcrystalline glass comprises spinel crystal phase with crystallinity more than 20%; the glass ceramics comprises the following components in percentage by mass: siO 35% or less 2 ≤55%、15%≤Al 2 O 3 ≤35%、0%≤Li 2 O<1%、0%≤MgO≤10%、0%≤Na 2 O≤15%、5%≤ZnO≤15%、0%≤ZrO 2 Less than or equal to 6 percent and 0 percent or less than or equal to TiO 2 Less than or equal to 6 percent; the microcrystalline glass comprises the following components in percentage by mass: siO (SiO) 2 +Al 2 O 3 ≥67%,3%≤ZrO 2 +TiO 2 ≤8%,MgO+ZnO≤16%,Li 2 O/(MgO+ZnO)≤0.11。
Description
Technical Field
The application relates to the technical field of glass, in particular to microcrystalline glass and reinforced glass as well as a preparation method and application thereof.
Background
With the continuous development of digital informatization in various industries, people put higher and higher demands on the weight reduction and service life of electronic display devices. Electronic cover glass is used as one of important materials for protecting the screen of display equipment from being in direct contact with the external environment, and has high requirements on optical and mechanical properties. The performance of the traditional common high-alumina glass is close to the limit interval of materials, the performance can be improved to a lower extent, and the microcrystalline glass has excellent mechanical properties due to the existence of crystalline phases, so that the use requirements of the market on cover plate glass in various environments and under different conditions can be met.
The prior glass ceramics in the market at present are mainly Lithium Aluminosilicate (LAS) systems, but the price of the required raw material lithium carbonate is too high, which limits the large-scale application of the glass ceramics of the system. In order to meet the market demand of glass ceramics, there are also some researches for improving the glass ceramics process, for example, CN202111056618.6 provides a transparent magnesium aluminum silicon glass ceramics, but the glass has a melting temperature higher than 1650 ℃ and a hardness lower than 714HV, and Sb is added 2 O 3 Non-environment-friendly clarifying agents; CN202010009864.5 and CN202210737448.6 both provide spinel transparent glass ceramics, but also have the problem of high melting temperature and transmittanceThe ion exchange depth and the mechanical property after strong chemical conversion are poor.
Disclosure of Invention
Based on the above, the application provides the microcrystalline glass which can reduce the melting temperature and improve the transmittance of the glass and the preparation method thereof.
Further, an embodiment of the present application also provides a tempered glass capable of improving ion exchange depth and mechanical properties, and a method for preparing the same.
Furthermore, the embodiment of the application also provides the application of the microcrystalline glass and the reinforced glass.
An embodiment of the application provides microcrystalline glass, which comprises spinel crystal phase with crystallinity more than 20%;
the glass ceramics comprises the following components in percentage by mass:
35%≤SiO 2 ≤55%、
15%≤Al 2 O 3 ≤35%、
0%≤Li 2 O<1%、
0%≤MgO≤10%、
0%≤Na 2 O≤15%、
5%≤ZnO≤15%、
0%≤ZrO 2 less than or equal to 6 percent
0%≤TiO 2 ≤6%;
The microcrystalline glass comprises the following components in percentage by mass:
SiO 2 +Al 2 O 3 ≥67%,3%≤ZrO 2 +TiO 2 ≤8%,
MgO+ZnO≤16%,Li 2 O/(MgO+ZnO)≤0.11。
in one embodiment, the glass-ceramic further comprises a zirconia crystal phase and/or a spodumene crystal phase.
In one embodiment, the glass-ceramic comprises the zirconia crystal phase, the zirconia crystal phase having a crystallinity of < 15%.
In one embodiment, the glass-ceramic contains the spodumene crystalline phase with a crystallinity of < 0.5%.
In one embodiment, the average grain diameter is 10nm to 70nm.
In one embodiment, the glass-ceramic comprises the following components in percentage by mass:
40%≤SiO 2 ≤55%、
20%≤Al 2 O 3 ≤35%、
0%≤Li 2 O<1%、
1%≤MgO≤8%、
2%≤Na 2 O≤13%、
5%≤ZnO≤12%、
2%≤ZrO 2 less than or equal to 6 percent
0%≤TiO 2 ≤6%。
The embodiment of the application provides a preparation method of microcrystalline glass, which comprises the following steps:
weighing glass raw materials according to the composition of the microcrystalline glass in any embodiment;
melting the raw materials to prepare a glass melt;
casting and molding the glass melt to prepare matrix glass;
and carrying out microcrystallization treatment on the base glass to prepare the microcrystalline glass.
The embodiment of the application also provides a preparation method of the reinforced glass, which comprises the following steps:
and carrying out chemical strengthening treatment on the microcrystalline glass in any embodiment.
The embodiment of the application also provides reinforced glass, which is prepared by the preparation method in the embodiment.
An embodiment of the application also provides a glass-ceramic as described in any of the above embodiments, or a tempered glass as described in any of the above embodiments, for use in the preparation of a glass article.
The glass ceramic is composed of glass with specific mass percentage, spinel is used as a main crystal phase, the glass ceramic can be prepared through a lower melting temperature, the average transmittance of the glass ceramic is high, the haze is low, and after chemical strengthening, the formed strengthened glass has high ion strengthening depth and good mechanical property.
Drawings
FIG. 1 is a diagram showing the morphology of a crystalline phase SEM of a glass ceramic sample of example 1;
fig. 2 is an XRD pattern of the glass ceramic sample of example 4.
Detailed Description
In order that the application may be readily understood, a more particular description of the application will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
Some embodiments of the present application provide a glass-ceramic comprising a spinel phase having a crystallinity of > 20%.
Spinel, e.g. magnesia-alumina, zincate-alumina, magnesia-zincate spinel, etc., are of the general formula AB 2 O 4 And a crystal oxide of cubic basic spinel structure, the prototype spinel structure being magnesium aluminate (MgAl 2 O 4 ). In the basic spinel structure, O atoms fill face-centered cubic (FCC) array sites, and the spinel structure has extremely high mechanical properties, and the control of the crystallinity of the spinel main crystal phase to be more than 20 percent can lead the microcrystalline glass to beAnd the strengthened glass has higher mechanical strength.
The glass ceramics comprises the following components in percentage by mass:
35%≤SiO 2 ≤55%、
15%≤Al 2 O 3 ≤35%、
0%≤Li 2 O<1%、
0%≤MgO≤10%、
0%≤Na 2 O≤15%、
5%≤ZnO≤15%、
0%≤ZrO 2 less than or equal to 6 percent
0%≤TiO 2 ≤6%。
The mass percentage of the compositions of the microcrystalline glass meets the following conditions:
SiO 2 +Al 2 O 3 ≥67%,3%≤ZrO 2 +TiO 2 ≤8%,
MgO+ZnO≤16%,Li 2 O/(MgO+ZnO)≤0.11。
in some embodiments of the application, the glass ceramics comprises 35 to 55 mass percent of SiO 2 。SiO 2 Is used as the main oxide for forming glass and can be used for stabilizing the network structure of microcrystalline glass by limiting SiO 2 The content of (2) in the above range can control the melting temperature (200 poise temperature) of the glass raw material, and avoid the excessively high or excessively low melting temperature. Preferably, the microcrystalline glass comprises 40 to 55 mass percent of SiO 2 。
In some embodiments of the application, the glass ceramics comprises 15 to 35 percent by mass of Al 2 O 3 。Al 2 O 3 The glass network can also be stabilized and also has the effect of improving the mechanical properties and chemical durability of the glass. Control of Al 2 O 3 The mass percentage of (2) is in a proper range, ensure that Al 2 O 3 Is sufficiently high to form a spinel phase, and the residual glassy phase also contains Al 2 O 3 Can be used for enhancing Li-Na and Na-K ionsCapacity of exchange; at the same time due to Al 2 O 3 Can be used as a network intermediate by adjusting Al 2 O 3 Can achieve control of the glass melt viscosity if Al 2 O 3 Too high a content of (C) results in an increase in melt viscosity, resulting in a decrease in glass forming ability of the glass melt, thereby controlling Al 2 O 3 The mass percentage of the glass is in a proper range, so that the glass melt can be ensured to have proper melt temperature, and the glass forming capability is good. Preferably, the microcrystalline glass comprises 20 to 35 mass percent of Al 2 O 3 . Further, controlling mass percent SiO 2 +Al 2 O 3 And the glass ceramic is more than or equal to 67 percent, and the enough stability of the glass ceramic structure can be ensured. In some embodiments of the application, the glass-ceramic composition contains MgO and ZnO. MgO and ZnO are alkaline earth metal oxides, and by using the alkaline earth metal oxides, the high-temperature viscosity of the base glass can be reduced, and the glass structure body can be modified, so that the strength and chemical stability of the base glass are improved, and MgO is also one of important constituent components of spinel in a main crystal phase. Further, if the mass percentage of MgO is 0% -10%, if the content of MgO is too high, the high-temperature viscosity of the melt will increase, so that the melting difficulty becomes high, the generation process of spinel crystal phase becomes difficult to control, the crystal grain generation size is too large, and the transmittance of glass is not improved. Preferably, the mass percentage of MgO is 1-8%. Further, the mass percentage of ZnO is 5-12%, because of Zn 2+ The glass melt has high field strength accumulation effect, the addition of ZnO can increase crystallization tendency of matrix glass and reduce crystallization activation energy of spinel crystal phase, but ZnO raw materials are more expensive, and if the addition amount is too high, the crystallization tendency of glass is increased as the addition amount of MgO is, the growth process of crystal phase is difficult to control during crystallization heat treatment, and the crystal size is extremely easy to be oversized. In addition, znO remains in a large amount in the glass phase, which deteriorates the glass properties and also lowers the Li-Na and Na-K ion exchange capacity. Thus, mgO+ZnO is controlled to be 16 or less.
The mg-al-si system glasses have a lower tendency to devitrify and a higher devitrify barrier, and in some embodiments of the application TiO 2 And ZrO(s) 2 The nucleating agent is added, so that the crystallization capacity of glass melt and the liquidus temperature can be improved in the preparation process of glass. Further, the microcrystalline glass comprises ZrO with the mass percentage of 0-6 percent 2 0 to 6 percent of TiO 2 By adding an appropriate amount of TiO 2 And/or ZrO 2 Can reduce crystallization activation energy, promote uniform crystal nucleus precipitation in the matrix glass and generate target crystalline phase. But TiO 2 The glass has extremely strong coloring capability, can have darker color, and is not suitable for being excessively added; at the same time, a higher content of TiO 2 The crystal phase growth in the matrix glass is difficult to control, the abnormal growth is carried out, more impurity phases are generated, the performance of the microcrystalline glass or the reinforced glass is difficult to control, and the phenomena of cracking and great performance reduction are easy to occur. ZrO (ZrO) 2 The solubility in glass melt is low, the melting temperature is extremely high, excessive ZrO is not suitable to be added, and the content is too high 2 The crystal phase growth in the matrix glass is difficult to control, the abnormal growth is caused, and more impurity phases are generated. Preferably, the microcrystalline glass comprises ZrO 2 to 6 mass percent 2 0 to 6 percent of TiO 2 . In order to ensure that a plurality of spinel, zirconia, spodumene and other crystal phases with uniform distribution and nanometer size are simultaneously precipitated in the matrix glass, the microcrystalline glass has high transmittance, and ZrO is further limited 2 And TiO 2 The mass percentage relation of (2) satisfies 3 percent or less of ZrO 2 +TiO 2 ≤8%。
Meanwhile, in some embodiments of the application, by limiting Li 2 The mass percentage relation between O and MgO, znO satisfies Li 2 Under the condition that O/(MgO+ZnO) is less than or equal to 0.11 and the above relation is met, the content of spodumene crystal phase can be effectively controlled, so that the microcrystalline glass has excellent optical performance, the alkali metal ion exchange capacity in the glass can be effectively balanced, and the reinforced glass obtained after chemical reinforcement has good stress performance.
Li 2 O and Na 2 The introduction of O is beneficial to lowering the melting temperature of the glass and is beneficial to subsequent ion exchange. Wherein the lithium ions are due to their ionic halfThe particle diameter is small, the accumulation effect is strong, the precipitation of a target crystalline phase is facilitated to a certain extent, but the content is too high, a large amount of spodumene crystalline phase is precipitated, the precipitation of spinel crystalline phase is inhibited, the sample transmittance is reduced, the performance is reduced, and preferably Li in the composition of glass ceramics 2 The mass percentage of O is 0-1%. Na (Na) 2 Excessive O introduction can inhibit the precipitation of spinel target crystal phase, is unfavorable for crystal phase control, is easy to precipitate heterogeneous phases such as albite, nepheline and the like, and can lead the sample to devitrify and reduce the performance, preferably Na in the composition of microcrystalline glass 2 O is 0-15% by mass, more preferably Na 2 The mass percentage of O is 2-13%.
In one embodiment, the glass-ceramic further comprises a zirconia crystal phase and/or a spodumene crystal phase. The zirconia crystal has extremely high mechanical property (Mohs hardness is more than 7.5), and is an ideal reinforced and toughened crystalline phase in microcrystalline glass. Spodumene LiAlSi 2 O 6 Belongs to monoclinic system, the crystal is columnar, granular or plate-shaped, the symmetry is 2/m, the crystal structure is similar to diopside, the crystal is one of main lithium-containing minerals, also called 2-spodumene, the microcrystalline glass contains spodumene crystal phase, and can be chemically strengthened in salt bath, wherein Na + And/or K + Will replace Li in spodumene structure + So that the surface of the glass is compressed and strengthened, and the overall strength can be greatly improved.
Further, the glass ceramic contains a zirconia crystal phase, and the crystallinity of the zirconia crystal phase is less than 15%. ZrO (ZrO) 2 The glass is added as a nucleating agent in the glass composition, and the excessive content of crystalline phase easily causes that the grain size of the glass is difficult to control, and transparent microcrystalline glass cannot be obtained, so that the crystallinity of zirconia is controlled to be less than 15 percent.
Further, the glass ceramic contains spodumene crystal phase, and the crystallinity of the spodumene crystal phase is less than 0.5%. The crystallinity of spodumene is controlled to be less than 0.5wt percent, so that the influence on the optical performance of glass caused by excessive content of spodumene crystal phase, such as increase of haze, reduction of transmittance and the like, can be avoided.
In some embodiments of the application, the average grain diameter is 10nm to 70nm. Controlling the average grain size within a specific range can avoid deterioration of the optical properties of the glass, such as an increase in haze, a decrease in transmittance, etc., due to an excessively large grain size.
In some embodiments of the present application, the composition of the glass-ceramic comprises, in mass percent:
40%≤SiO 2 ≤55%、
20%≤Al 2 O 3 ≤35%、
0%≤Li 2 O<1%、
1%≤MgO≤8%、
2%≤Na 2 O≤13%、
5%≤ZnO≤12%、
2%≤ZrO 2 less than or equal to 6 percent
0%≤TiO 2 ≤6%。
Some embodiments of the present application provide a method for preparing glass ceramics, which includes the following steps S110 to S140.
S110: glass raw materials were weighed according to the composition of the glass ceramics in any of the above examples.
The glass composition including SiO of 35 percent or less can be obtained by using the glass raw materials according to the mass percent 2 ≤55%、15%≤Al 2 O 3 ≤35%、0%≤Li 2 O<1%、0%≤MgO≤10%、0%≤Na 2 O≤15%、5%≤ZnO≤15%、0%≤ZrO 2 Less than or equal to 6 percent and 0 percent or less than or equal to TiO 2 ≤6%;
And the mass percentage of the compositions of the microcrystalline glass meets the following conditions: siO (SiO) 2 +Al 2 O 3 ≥67%,3%≤ZrO 2 +TiO 2 ≤8%,MgO+ZnO≤16%,Li 2 O/(MgO+ZnO)≤0.11。
S120: and melting the raw materials to prepare a glass melt.
Further, the melting temperature is 1300-1550 ℃.
Further, the melting time is 6-10 h.
Further, stirring may also be performed during the melting process.
S130: and casting and forming the glass melt to prepare the matrix glass.
Further, the step of cooling the glass melt may be included prior to casting. Preferably, the temperature is reduced to 1200-1450 ℃, and the temperature is kept for 2h for homogenization.
Further, the method may further comprise a step of preheating the mold before casting. Preferably, the mold is preheated to 400-500 ℃.
Further, after the casting molding, a step of annealing the molded glass may be further included. Preferably, the annealing conditions include: preserving heat for 1.5-2.5 h at 400-500 ℃, and then controlling the cooling rate to 130-150 ℃ within 5-7 h.
Further, the annealing may further include a step of natural cooling.
S140: and (3) carrying out microcrystallization treatment on the base glass to prepare microcrystalline glass.
Further, the step of microcrystallizing treatment includes: the substrate glass is subjected to heat treatment and nucleation, and then the temperature is raised and crystallized.
Further, the nucleation temperature is 600-800 ℃.
Further, the nucleation time is 0.5-10 h.
Further, the crystallization temperature is 700-900 ℃.
Further, the crystallization time is 0.1 to 4 hours.
It will be appreciated that the glass-ceramic provided by the present application may be prepared by conventional glass processes including, for example, but not limited to, float forming processes, overflow downdraw processes, draw-up processes, flat draw processes, calendaring processes, and the like.
Some embodiments of the present application also provide a method for preparing tempered glass, comprising the steps of:
and carrying out chemical strengthening treatment on the microcrystalline glass in any embodiment.
Further, the chemical strengthening treatment includes two chemical strengthening.
Further, the step of the first chemical strengthening treatment comprises: the glass ceramics are placed in a first molten liquid formed by at least one of sodium nitrate and potassium nitrate for soaking.
Preferably, the mass ratio of sodium nitrate to potassium nitrate in the first melt is (40-100): 0-60.
Preferably, the soaking conditions of the first chemical strengthening treatment include: the soaking temperature is 440-500 ℃ and the soaking time is 4-16 h.
Further, the step of the second chemical strengthening treatment comprises: the glass after the first chemical strengthening is placed in a second molten liquid formed by at least one of sodium nitrate and potassium nitrate to be soaked.
Preferably, the mass ratio of sodium nitrate to potassium nitrate in the second melt is (96-100): 4-0.
Preferably, the soaking conditions of the second chemical strengthening treatment include: the soaking temperature is 380-440 ℃ and the soaking time is 1-4 h.
Some embodiments of the present application also provide a tempered glass prepared by the preparation method in the above embodiments.
Some embodiments of the application also provide a glass-ceramic as in any of the embodiments above, or a strengthened glass as in any of the embodiments above, for use in making a glass article.
It is understood that the glass article may be, for example, but not limited to, an electronic glass, a cover glass, an optoelectronic glass, a fire-resistant glass, a construction glass or other specialty glass, and the like.
In some embodiments of the application, the average transmittance of the glass ceramics is more than or equal to 85 percent, and the haze is less than or equal to 1.8. After chemical strengthening, the strengthened glass obtained by the application can achieve the excellent performances that the compressive stress CS30 with the depth of 30 μm exceeds 50MPa, the overall compressive stress depth dol_0 exceeds 100 μm, the surface Mohs hardness exceeds 7.5, the ring pressure intensity exceeds 823MPa, and the falling height of the complete machine sand paper exceeds 1.6 m.
The glass ceramics and the tempered glass of the present application, and the preparation method and application thereof are described in detail below by way of specific examples. The following embodiments are more specific, and it is understood that in other embodiments, this is not limiting. In the following examples, the instruments, reagents and materials involved, unless otherwise specified, are conventional instruments, reagents and materials already known in the art and are commercially available. The experimental methods, detection methods, and the like in the examples described below are conventional experimental methods and detection methods known in the prior art unless otherwise specified.
1. Preparing base glass:
the glass compositions of examples 1 to 20 and comparative examples 1 to 4 were prepared by weighing the respective glass raw materials according to the glass compositions of examples, mixing them well, melting them in a platinum crucible at 1450℃for 8 hours to form a glass melt, and stirring them in a platinum stirring paddle; after the stirring paddle is pulled out, the glass melt is cooled to 1320 ℃, and the temperature is kept for 2 hours for homogenization; and then casting the glass melt onto an iron mold to form glass blocks with the size of 80mm multiplied by 160mm, preheating to 450 ℃ before casting the mold, immediately transferring the glass blocks into an annealing furnace for annealing after hardening, preserving heat for 2 hours, controlling the temperature to be reduced to 140 ℃ for 6 hours, naturally cooling to obtain matrix glass, and taking out for later use.
The substrate glass samples of examples 1 to 20 and comparative examples 1 to 4 were cut into glass sheets of 70mm×140mm×0.6mm by a STX-1203 wire cutter for Shenyang crystal, thinned and polished by a HD-640-5L double-sided grinding polisher of Shenzhen Haiden, and then subjected to CNC edging, and transmittance in the wavelength range of 380nm to 780nm was measured by using a Lambda950 ultraviolet-visible spectrophotometer by Perkinelmer company, U.S. and the results are shown in tables 1 to 3.
2. Preparation of microcrystalline glass
The base glass obtained in step 1 of examples 1 to 20 and comparative examples 1 to 4 was subjected to microcrystallization treatment according to the microcrystallization process parameters shown in tables 1 to 3 to prepare a glass ceramic.
The microcrystalline glass samples obtained after crystallization of examples 1 to 20 and comparative examples 1 to 4 were cut, and the sections were ground and polished for use. The above glass ceramics sample was cut into 20mm×20mm, and its crystal phase type was tested by Bruker X-ray diffractometer Bruker D8 advance, and its crystal phase ratio and amorphous phase ratio of different types were calculated by its TOPAS software simulation, and recorded in tables 1 to 3.
3. Preparation of strengthened glass
The microcrystalline glasses prepared in the step 2 of the examples 1 to 20 and the comparative examples 1 to 4 are subjected to a secondary strengthening process to prepare strengthened glass.
First chemical strengthening: the glass ceramics are placed in a first molten liquid formed by at least one of sodium nitrate and potassium nitrate to be soaked, and the mass percentages of the sodium nitrate and the potassium nitrate in the first molten liquid and the soaking conditions are as shown in the following tables 1 to 3.
Second chemical strengthening: the glass after the first chemical strengthening is placed in a second molten liquid formed by at least one of sodium nitrate and potassium nitrate to be soaked, and the mass percentages of the sodium nitrate and the potassium nitrate in the second molten liquid and the soaking conditions are as shown in the following tables 1 to 3.
The reinforced glass prepared in examples 1 to 20 and comparative examples 1 to 4 was tested by SLP2000 surface stress meter of Japanese folding primitive Industrial Co., ltd., li-Na exchanged compressive stress CS30 of 30 μm depth and stress depth Dol-0 (. Mu.m), the surface Viomo hardness was tested by Mohs hardness pen, the transmittance in the wavelength range of 380nm to 780nm was tested by Lambda950 ultraviolet-visible spectrophotometer of Perkinelmer Co., U.S.A., the haze was tested by SUGA optical HZ-V3 haze meter, the ring crush strength was tested by PT-307A universal tester of Prufite (upper ringLower ring) The drop height of the 180-mesh sand paper is tested by adopting a Shenzhen high GP-2112-T directional drop tester and recorded in the following tables 1 to 3.
TABLE 1 glass compositions, process parameters, performance data for examples 1-10
TABLE 2 glass compositions, process parameters, performance data for examples 11-20
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TABLE 3 glass compositions, process parameters, performance data for comparative examples 1-4
As is clear from tables 1 to 3, the glass ceramics of examples 1 to 20 have spinel as the main crystal phase, have high average transmittance and low haze, and after chemical strengthening, the resulting strengthened glass has high ion strengthening depth and good mechanical properties.
In comparative example 1, li 2 O is 2% by mass, more than 0.95% by mass, and
Li 2 o/(mgo+zno) =0.15, greater than 0.11; the crystal phase and the grain size of spodumene which are more precipitated after crystallization become larger, so that the transmittance of glass is reduced, the haze is increased, and the ring pressure and the anti-drop performance are finally reduced after ion reinforcement.
The mass percentage of MgO in comparative example 2 was 13%, more than 10%, mgo+zno=18%, more than 16%, siO 2 +Al 2 O 3 =65%, less than 67%; the content of magnesia is increased, the content of silica and alumina is reduced, the generation difficulty of the impurity phase is reduced, more periclase impurity phase is precipitated, the generation of spinel target crystal phase is inhibited, the grain size is enlarged, the transmittance of a sample is reduced, the haze is enlarged, and the ion strengthening is finally reflected as the strengthening stress, the ring pressure and the anti-drop performance are reduced.
The mass percentage of ZnO in comparative example 3 is 2%, less than 5%, tiO 2 Is 8% by mass, more than 6% by mass, zrO 2 +TiO 2 =10%, greater than 8%; the zinc oxide content is reduced, so that the spinel crystallization tendency is weakened, periclase impurity phase is easy to generate, the grain size is enlarged, and the transmittance of the periclase is difficult to control. In addition, the content of the titanium oxide nucleating agent is increased, the crystallization tendency is increased, periclase impurity phase is easy to occur, the grain size is difficult to control, and the content of titanium oxide is too high, so that glass is colored, and the transmittance of the glass is affected; the final appearance of the reinforced ion is the reduction of the reinforced stress, ring pressure and anti-drop performance.
ZrO in comparative example 4 2 +TiO 2 The content of the nucleating agent is lower than 3%, the crystallization tendency of the glass sample is low, crystalline phases cannot be precipitated, and the final appearance of the glass sample after ion reinforcement is lower in reinforcement stress, ring pressure and anti-drop performance.
Fig. 1 shows a morphology diagram of a crystalline phase SEM scanning electron microscope of the microcrystalline glass sample of example 1, and fig. 1 shows that the glass has a microcrystalline structure.
Fig. 2 shows XRD patterns of the glass ceramic sample of example 4, and it can be seen from fig. 2 that example 4 contains both spinel and zirconia crystal phases, and spinel is the predominant crystal phase.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. The microcrystalline glass is characterized by comprising spinel crystal phases with crystallinity more than 20%;
the glass ceramics comprises the following components in percentage by mass:
35%≤SiO 2 ≤55%、
15%≤Al 2 O 3 ≤35%、
0%≤Li 2 O<1%、
0%≤MgO≤10%、
0%≤Na 2 O≤15%、
5%≤ZnO≤15%、
0%≤ZrO 2 less than or equal to 6 percent
0%≤TiO 2 ≤6%;
The microcrystalline glass comprises the following components in percentage by mass:
SiO 2 +Al 2 O 3 ≥67%,3%≤ZrO 2 +TiO 2 ≤8%,
MgO+ZnO≤16%,Li 2 O/(MgO+ZnO)≤0.11。
2. the glass-ceramic according to claim 1, further comprising a zirconia crystal phase and/or a spodumene crystal phase.
3. The glass-ceramic according to claim 2, wherein the glass-ceramic contains the zirconia crystal phase, and the crystallinity of the zirconia crystal phase is < 15%.
4. The glass-ceramic according to claim 2, wherein the glass-ceramic contains the spodumene crystal phase, and the crystallinity of the spodumene crystal phase is < 0.5%.
5. The glass-ceramic according to any one of claims 1 to 4, wherein the average grain diameter is 10nm to 70nm.
6. The glass-ceramic according to any one of claims 1 to 4, wherein the composition of the glass-ceramic comprises, in mass percent:
40%≤SiO 2 ≤55%、
20%≤Al 2 O 3 ≤35%、
0%≤Li 2 O<1%、
1%≤MgO≤8%、
2%≤Na 2 O≤13%、
5%≤ZnO≤12%、
2%≤ZrO 2 less than or equal to 6 percent
0%≤TiO 2 ≤6%。
7. The preparation method of the glass ceramics is characterized by comprising the following steps:
weighing glass raw materials according to the composition of the glass ceramics according to any one of claims 1 to 6;
melting the raw materials to prepare a glass melt;
casting and molding the glass melt to prepare matrix glass;
and carrying out microcrystallization treatment on the base glass to prepare the microcrystalline glass.
8. A method for producing tempered glass, comprising the steps of:
a glass ceramic according to any one of claims 1 to 6 is subjected to a chemical strengthening treatment.
9. A tempered glass produced by the production method according to claim 8.
10. Use of a glass ceramic according to any one of claims 1 to 6, or a strengthened glass according to claim 9, for the preparation of a glass article.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5968857A (en) * | 1997-03-31 | 1999-10-19 | Corning Incorporated | Glass-ceramics |
CN111018354A (en) * | 2020-01-06 | 2020-04-17 | 武汉理工大学 | Spinel transparent glass-ceramic with low melting temperature and preparation and performance enhancement method thereof |
CN114907014A (en) * | 2020-06-29 | 2022-08-16 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and manufacturing method thereof |
CN115010369A (en) * | 2022-06-27 | 2022-09-06 | 武汉理工大学 | Chemically-strengthened spinel microcrystalline glass and preparation method and application thereof |
WO2022228583A1 (en) * | 2021-04-28 | 2022-11-03 | 深圳晶酝科技有限公司 | Glass-ceramic material, preparation method therefor and application thereof in semiconductor devices |
CN115286251A (en) * | 2022-08-10 | 2022-11-04 | 清远南玻节能新材料有限公司 | Tempered glass, microcrystalline glass and preparation method and application thereof |
CN116375345A (en) * | 2023-04-27 | 2023-07-04 | 成都光明光电股份有限公司 | Glass ceramics and glass ceramics products having spinel crystal phase |
CN116621455A (en) * | 2023-04-27 | 2023-08-22 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and method for producing the same |
-
2023
- 2023-08-31 CN CN202311109673.6A patent/CN117125897A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5968857A (en) * | 1997-03-31 | 1999-10-19 | Corning Incorporated | Glass-ceramics |
CN111018354A (en) * | 2020-01-06 | 2020-04-17 | 武汉理工大学 | Spinel transparent glass-ceramic with low melting temperature and preparation and performance enhancement method thereof |
CN114907014A (en) * | 2020-06-29 | 2022-08-16 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and manufacturing method thereof |
WO2022228583A1 (en) * | 2021-04-28 | 2022-11-03 | 深圳晶酝科技有限公司 | Glass-ceramic material, preparation method therefor and application thereof in semiconductor devices |
CN115010369A (en) * | 2022-06-27 | 2022-09-06 | 武汉理工大学 | Chemically-strengthened spinel microcrystalline glass and preparation method and application thereof |
CN115286251A (en) * | 2022-08-10 | 2022-11-04 | 清远南玻节能新材料有限公司 | Tempered glass, microcrystalline glass and preparation method and application thereof |
CN116375345A (en) * | 2023-04-27 | 2023-07-04 | 成都光明光电股份有限公司 | Glass ceramics and glass ceramics products having spinel crystal phase |
CN116621455A (en) * | 2023-04-27 | 2023-08-22 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and method for producing the same |
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